CN114921257B - Method for improving quality of oil shale pyrolysis oil through deep pyrolysis - Google Patents
Method for improving quality of oil shale pyrolysis oil through deep pyrolysis Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
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Abstract
The invention discloses a method for improving the quality of oil shale pyrolysis oil through deep pyrolysis, and belongs to the technical field of new energy. The supercritical water and oil shale sample dissolved with bimetallic catalyst are pyrolyzed in a primary pyrolysis unit, primary pyrolysis volatile matter enters a secondary pyrolysis unit through a pipeline with a heating sleeve, and the primary pyrolysis volatile matter, the catalyst and supercritical CO2Performing secondary pyrolysis and supercritical CO2The thermal decomposition oil has strong diffusion coefficient and viscosity reduction characteristic, is fully fused with pyrolysis volatile matters, and inhibits the formation of coke and gas, thereby achieving the purpose of improving the quality of the pyrolysis oil twice. The method uses bimetallic catalyst dissolved in supercritical water to provide hydrogenation active sites, enhances the hydrogenation effect on oil shale pyrolysis, generates synergistic effect, and passes through supercritical CO2And the catalyst is subjected to secondary pyrolysis, so that deep pyrolysis of the oil shale pyrolysis oil is realized.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a method for improving the quality of oil shale pyrolysis oil through deep pyrolysis.
Background
As an unconventional energy source, the oil shale has abundant resources all over the world. The total amount of the Chinese oil shale resource is the second place in the world, and is converted into oil shale oil which is about 62 percent of the amount of the conventional petroleum resource in China. The method for preparing light oil products from the oil shale pyrolysis oil is the one with the lowest cost in the current method for preparing qualified liquid fuel from artificial petroleum.
Supercritical water is water in which the density of water expanded by high temperature and the density of water vapor compressed by high pressure are exactly the same when the pressure and temperature of the water reach a certain value, and has a strong solvation effect and a displacement effect. Lu et al studied the pyrolysis behavior and product characteristics of oil shale smoothed by supercritical water at 450 deg.C and 27MPa, and found that the yield of oil discharged from supercritical water pyrolysis at 450 deg.C was 14.33 times that of anhydrous pyrolysis, but the heavy oil content was high, and the colloid and asphaltene content was 65.77%.
The high heavy component of pyrolysis oil limits the application of supercritical water in the field of extraction of oil and gas from oil shale pyrolysis, and therefore, a method for upgrading oil shale pyrolysis oil through deep pyrolysis is needed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for improving oil shale pyrolysis oil by utilizing deep pyrolysis, so as to achieve the aim of doubly improving the quality of the pyrolysis oil.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for improving the quality of oil shale pyrolysis oil through deep pyrolysis comprises the following steps:
crushing and screening an oil shale sample, and then placing the oil shale sample in a primary pyrolysis unit;
step two, continuously introducing supercritical water dissolved with a bimetallic catalyst into the primary pyrolysis unit, and after carrying out pyrolysis reaction for 1-8 hours, introducing obtained pyrolysis volatile matters into a secondary pyrolysis unit in which the catalyst is placed in advance through a pipeline with a heating sleeve; the bimetallic catalyst is any two of sulfate, carbonate, acetate and nitrate of alkali metals K and Na;
step three, continuously introducing supercritical CO into the secondary pyrolysis unit2Carrying out secondary pyrolysis with the primary pyrolysis volatile matter and a catalyst placed in advance, reacting for 0.2-1.2h,and cooling and collecting the pyrolysis oil gas of the secondary pyrolysis product.
Further, in the second step, the mass ratio of two metal catalysts in the bimetallic catalyst dissolved in supercritical water is 1: (1-5).
Furthermore, in the second step, the temperature of the supercritical water is controlled to be 374-500 ℃, and the pressure is controlled to be 23-30 Mpa.
Further, in the second step, the mass ratio of the bimetallic catalyst to the oil shale sample in the primary pyrolysis unit is 1: (6-15).
Further, in the second step, the ratio of the mass of the bimetallic catalyst dissolved in the supercritical water to the volume of the supercritical water is (1.
Further, in the second step, the temperature of the pipeline with the heating jacket is controlled to be 200-300 ℃.
Further, in the second step, the catalyst in the secondary pyrolysis unit is one or more of active metals of sulfate, carbonate, acetate and nitrate of Ba, fe and Ce.
Further, the mass ratio of the catalyst to the oil shale sample in the secondary pyrolysis unit is 1: (9-20).
Further, in step three, the supercritical CO2The temperature is controlled between 410 ℃ and 500 ℃, and the pressure is controlled between 8Mpa and 12Mpa.
Further, the oil shale sample quality and the supercritical CO described in step three2The volume ratio of (1.
The invention utilizes the strong solvation effect and the displacement effect of supercritical water to fully dissolve the bimetallic catalyst, generates a synergistic effect, provides hydrogenation active sites, and improves the content of light oil in the pyrolysis oil, thereby improving the quality of the pyrolysis oil. By using supercritical CO2Strong diffusion coefficient and viscosity reduction property, and realizes the secondary upgrading of the pyrolysis oil by mixing with the catalyst.
The deep pyrolysis reaction system adopted by the invention is divided into the primary pyrolysis unit and the secondary pyrolysis unit, and can continuously realize double promotion of the quality of the oil shale pyrolysis oil.
Drawings
FIG. 1 is a schematic diagram of the apparatus for upgrading oil shale pyrolysis oil by deep pyrolysis according to the present invention.
In fig. 1, 1-primary pyrolysis unit, 2-connecting pipeline, 3-heating jacket, 4-temperature monitoring device, 5-pressure monitoring device, 6-catalyst, 7-secondary pyrolysis unit, 8-switch valve, 9-gas collecting bag, and 10-cold water bath device.
FIG. 2 is a graph comparing the light oil content, medium oil content and heavy oil content of example 3 and comparative examples 1-4.
Detailed Description
An exemplary embodiment of the present invention provides a method for improving the quality of oil shale pyrolysis oil through deep pyrolysis, comprising the following steps:
step one, crushing and screening an oil shale sample, and then placing the oil shale sample in a primary pyrolysis unit.
Preferably, the oil shale sample is crushed and sieved to 13-60mm.
And step two, continuously introducing supercritical water dissolved with a bimetallic catalyst into the primary pyrolysis unit, and after carrying out pyrolysis reaction for 1-8h, introducing the obtained pyrolysis volatile matter into a secondary pyrolysis unit in which the catalyst is placed in advance through a pipeline with a heating sleeve.
The bimetallic catalyst is any two of sulfate, carbonate, acetate and nitrate of alkali metals K and Na. Alkali metal has strong reactivity, and alkali metal salt can generate synergistic effect when dissolved in supercritical water to provide hydrogenation effect. The mass ratio of two metal catalysts in the bimetallic catalyst dissolved in supercritical water is 1: (1-5), the mass ratio of the bimetallic catalyst to the oil shale sample is 1: (6-15).
In this step, preferably, the ratio of the mass of the bimetallic catalyst dissolved in supercritical water to the volume of supercritical water is (1. The temperature of the supercritical water is controlled to be 374-500 ℃, and the pressure is controlled to be 23-30 Mpa.
In the step, the temperature of the pipeline with the heating sleeve is controlled to be 200-300 ℃, so that the primary pyrolysis product is kept at a certain temperature, the cooling is prevented, and the secondary pyrolysis effect is ensured.
In the step, the catalyst in the secondary pyrolysis unit is one or more of active metal sulfate, carbonate, acetate and nitrate of Ba, fe and Ce, and the catalyst is active in chemical property and is mixed with a volatile product of primary pyrolysis and supercritical CO2The reaction realizes the secondary quality improvement of the pyrolysis oil. The mass ratio of the catalyst to the oil shale sample is 1: (9-20).
Step three, continuously introducing supercritical CO into the secondary pyrolysis unit2And carrying out secondary pyrolysis with the primary pyrolysis volatile matter and a pre-placed catalyst, and after reacting for 0.2-1.2h, cooling and collecting pyrolysis oil gas of an obtained secondary pyrolysis product.
In this step, the supercritical CO2The temperature is controlled to be between 410 and 500 ℃, and the pressure is controlled to be between 8 and 12Mpa. Oil shale sample mass and supercritical CO2The volume ratio is (1.
The reaction time and temperature of the primary pyrolysis unit and the secondary pyrolysis unit in the reaction are suitable reaction conditions in an experiment, so that the quality of the pyrolysis oil is ensured, and the yield is ensured.
The above embodiment utilizes supercritical water and oil shale dissolved with bimetallic catalyst to pyrolyze in the primary pyrolysis unit, the primary pyrolysis volatile matter enters the secondary pyrolysis unit through the pipeline with heating jacket, and the primary pyrolysis volatile matter, catalyst and supercritical CO2Performing secondary pyrolysis and supercritical CO2The thermal decomposition oil has strong diffusion coefficient and viscosity reduction characteristic, is fully fused with pyrolysis volatile matters, and inhibits the formation of coke and gas, thereby achieving the purpose of improving the quality of the pyrolysis oil twice. The method uses a bimetallic catalyst to dissolve in supercritical water to provide a hydrogenation active site, so that the hydrogenation effect of the bimetallic catalyst on the pyrolysis of oil shale is enhanced, and a synergistic effect is generated; and by supercritical CO2And the catalyst is subjected to secondary pyrolysis, so that deep pyrolysis of the oil shale pyrolysis oil is realized.
As shown in FIG. 1, the above-described enhancement of oil shale pyrolysis by deep pyrolysisThe oil quality process is achieved by a deep pyrolysis system comprising a primary pyrolysis unit 1, a secondary pyrolysis unit 7, and a cooling collection unit. The primary pyrolysis unit 1 and the secondary pyrolysis unit 7 are pyrolysis reaction kettles, and the pyrolysis reaction kettles are provided with temperature monitoring devices 4 and pressure monitoring devices 5. A supercritical water input port dissolved with a catalyst is arranged on the primary pyrolysis unit 1, and the oil shale sample is placed in the primary pyrolysis unit 1; the secondary pyrolysis unit 7 is provided with oil supercritical CO2An input port, in which the catalyst 6 is previously placed in the secondary pyrolysis unit 7. The primary pyrolysis unit 1 and the secondary pyrolysis unit 7 are connected by a pipe 2 with a heating jacket 3. The cooling collection unit comprises a cold water bath device 10 and a gas collection bag 9, the cold water bath device 10 comprises a water bath and a gas collection bottle, the gas collection bottle is arranged in the water bath and connected with the pyrolysis oil gas outlet end of the secondary pyrolysis unit 7, and the gas collection bag 9 is connected with the gas collection bottle. The pipeline 2 is provided with a switch control valve 8.
Continuously introducing supercritical water dissolved with a bimetallic catalyst into the primary pyrolysis unit 1, opening a switch control valve 8 after a pyrolysis reaction is carried out for 1-8 hours, and allowing obtained pyrolysis volatile matters to enter a secondary pyrolysis unit 7 in which a catalyst 6 is placed in advance through a pipeline 2 with a heating sleeve 3; continuously introducing supercritical CO into the secondary pyrolysis unit 72And carrying out secondary pyrolysis with the primary pyrolysis volatile matter and a catalyst 6 placed in advance, reacting for 0.2-1.2h, and collecting pyrolysis oil gas of an obtained secondary pyrolysis product in a cooling collection unit, and then carrying out component analysis.
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
Crushing and screening the oil shale to 13mm by adopting compliant oil shale, placing 72g in a primary pyrolysis unit, and dissolving 10g of Na2SO4And 2gK2SO4The 1200ml supercritical water is continuously introduced into the primary pyrolysis unit, after the pyrolysis reaction is carried out for 8 hours, the temperature is 374 ℃, the pressure is 23Mpa, and the valve is openedAnd (3) allowing pyrolysis volatile matters to enter a secondary pyrolysis unit through a pipeline at 300 ℃, and continuously introducing 4320ml of supercritical CO into the secondary pyrolysis unit2With primary pyrolysis volatiles and pre-placed 8gBaCl2And (3) carrying out secondary pyrolysis, reacting for 0.2h at 500 ℃ under 12Mpa, and allowing pyrolysis oil gas of the obtained secondary pyrolysis product to enter a cooling unit and collecting the pyrolysis oil gas for component analysis. The result is that the pyrolysis oil contains 65% of light oil with C8-C12 atoms; 20% of medium oil with C12-C18, and C atoms>The C19 heavy oil accounted for 20%.
Example 2
Crushing and screening oil shale to 60mm by adopting smooth oil shale, placing 142.5g of the crushed oil shale in a primary pyrolysis unit, and dissolving 4.75g of KNO3And 4.75gNa2CO3380ml of supercritical water is continuously introduced into the primary pyrolysis unit, after the pyrolysis reaction is carried out for 1h, the temperature is 500 ℃, the pressure is 30Mpa, a valve is opened, pyrolysis volatile matters enter the secondary pyrolysis unit through a pipeline at 200 ℃, and 14250ml of supercritical CO is continuously introduced into the secondary pyrolysis unit2With primary pyrolysis volatiles and pre-conditioned 7.125gFe (NO)3)3And (3) carrying out secondary pyrolysis, reacting for 1.2h at the temperature of 410 ℃ and the pressure of 8Mpa, feeding the obtained secondary pyrolysis product pyrolysis oil gas into a cooling unit, and collecting and carrying out component analysis. The result is that the light oil with C8-C12 atoms in the pyrolysis oil accounts for 70 percent; the C12-C18 medium oil accounts for 12%, and has C atoms>The C19 heavy oil accounts for 6%, and the content of the light oil is improved by 18% compared with the content of the light oil in the conventional method.
Example 3
Crushing and screening the oil shale to 60mm by adopting compliant oil shale, placing 142.5g of the crushed oil shale in a primary pyrolysis unit, and dissolving 4.75g of KNO3And 4.75gNa2CO3380ml of supercritical water is continuously introduced into the primary pyrolysis unit, after the pyrolysis reaction is carried out for 5 hours, the temperature is 480 ℃, the pressure is 28Mpa, a valve is opened, pyrolysis volatile matters enter the secondary pyrolysis unit through a pipeline at 200 ℃, 14250ml of supercritical CO is continuously introduced into the secondary pyrolysis unit2With primary pyrolysis volatiles and pre-conditioned 7.125gFe (NO)3)3Carrying out secondary pyrolysis and reactionAfter 0.5h, the temperature is 500 ℃, the pressure is 12Mpa, and the obtained secondary pyrolysis product pyrolysis oil gas enters a cooling unit and is collected for component analysis. The result is that the pyrolysis oil contains 78% of light oil with C8-C12 atoms; 15% of medium oil with C12-C18 atoms, and C atoms>The C19 heavy oil accounted for 7%.
Example 4
Crushing and screening oil shale to 20mm by adopting smooth oil shale, placing 100g of crushed oil shale in a primary pyrolysis unit, and dissolving 2gK2SO4And 8gNaNO3The 600ml supercritical water continuously lets in the primary pyrolysis unit, after the pyrolysis reaction is carried out for 3h, the temperature is 460 ℃, the pressure is 25Mpa, the valve is opened, the pyrolysis volatile matter enters the secondary pyrolysis unit through the 230 ℃ pipeline, and 6000ml supercritical CO is continuously let in to the secondary pyrolysis unit2With primary pyrolysis volatiles and pre-deposited 10gCe (NO)3)3·6H2And performing secondary pyrolysis on the O, reacting for 0.6h at 480 ℃ under 10Mpa, and allowing the obtained secondary pyrolysis product pyrolysis oil gas to enter a cooling unit and collecting for component analysis. The result is that the light oil with C atoms of C8-C12 accounts for 68% of the pyrolysis oil; the C12-C18 medium oil accounts for 18%, and has C atoms>The C19 heavy oil accounted for 14%.
Example 5
Crushing and sieving oil shale to 20mm by using pacific oil shale, placing 50g in a primary pyrolysis unit, and dissolving 1.25g of NaNO in the oil shale3And 5gK2CO3625ml supercritical water continuously lets in first pyrolysis unit, and after pyrolytic reaction carried out 4h, the temperature was 430 ℃, and pressure was 24Mpa, opened the valve, and the pyrolysis volatile substance got into the secondary pyrolysis unit through 260 ℃'s pipeline, continuously lets in 3500ml supercritical CO to the secondary pyrolysis unit2With primary pyrolysis volatiles and pre-conditioned 5gFe2(SO4)3And (3) carrying out secondary pyrolysis, reacting for 0.4h at 480 ℃ under 11Mpa, and allowing the obtained secondary pyrolysis product pyrolysis oil gas to enter a cooling unit and collecting for component analysis. The result is that the pyrolytic oil contains 75% of light oil with C8-C12 atoms; 15% of medium oil with C12-C18 atoms, and C atoms>Weight of C19The mass oil accounts for 10 percent.
Example 6
Crushing and screening the oil shale to 30mm by adopting compliant oil shale, placing 70g of the crushed oil shale in a primary pyrolysis unit, and dissolving 1.75gK2SO4And 5.25gKNO3350ml supercritical water continuously let in the primary pyrolysis unit, after the pyrolysis reaction is carried out for 2 hours, the temperature is 500 ℃, the pressure is 30Mpa, a valve is opened, the pyrolysis volatile matter enters the secondary pyrolysis unit through a 240 ℃ pipeline, and 4200ml supercritical CO is continuously let in to the secondary pyrolysis unit2With primary pyrolysis volatiles and pre-deposited 7gCe (NO)3)3Ce(NO3)3·6H2And performing secondary pyrolysis on the O, reacting for 0.7h at 490 ℃ under 11Mpa, and allowing the obtained secondary pyrolysis product pyrolysis oil gas to enter a cooling unit and collecting for component analysis. As a result, 69% of the light oil with C8-C12 atoms in the pyrolysis oil is obtained; the C12-C18 medium oil accounts for 18.8%, and has C atoms>The C19 heavy oil accounted for 12.2%.
Example 7
Crushing and screening the oil shale to 40mm by adopting compliant oil shale, placing 120g of the crushed oil shale in a primary pyrolysis unit, and dissolving 1.75gK2SO4And 5.25gNa2CO3The 700ml supercritical water is continuously introduced into the primary pyrolysis unit, after the pyrolysis reaction is carried out for 6 hours, the temperature is 490 ℃, the pressure is 28Mpa, a valve is opened, the pyrolysis volatile matter enters the secondary pyrolysis unit through a 280 ℃ pipeline, and 7200ml supercritical CO is continuously introduced into the secondary pyrolysis unit2With the primary pyrolysis volatiles and pre-settled 6gFe (NO)3)3And (3) carrying out secondary pyrolysis, reacting for 1h at 460 ℃ and 10Mpa, and allowing the obtained secondary pyrolysis product pyrolysis oil gas to enter a cooling unit and collecting for component analysis. The result is that the pyrolysis oil contains 72% of light oil with C8-C12 atoms; the C12-C18 medium oil accounts for 19 percent>The C19 heavy oil accounted for 9%.
Example 8
Crushing and screening the oil shale to 40mm by adopting compliant oil shale, placing 90g of the crushed oil shale in a primary pyrolysis unit, and dissolving 3g of Na2CO3And 6gNa2SO4The 720ml supercritical water continuously lets in the primary pyrolysis unit, after the pyrolysis reaction is carried out for 4.5 hours, the temperature is 500 ℃, the pressure is 30Mpa, the valve is opened, the pyrolysis volatile matter enters the secondary pyrolysis unit through the pipeline with the temperature of 200 ℃, and 5400ml supercritical CO is continuously let in to the secondary pyrolysis unit2With primary pyrolysis volatiles and 4.5gFe previously placed2(SO4)3And carrying out secondary pyrolysis, reacting for 1.1h at 470 ℃ under 10Mpa, and allowing the obtained secondary pyrolysis product pyrolysis oil gas to enter a cooling unit and collecting for component analysis. The result is that the pyrolysis oil contains 73.5% of light oil with C8-C12 atoms; 20% of medium oil with C12-C18, and C atoms>The C19 heavy oil accounted for 6.5%.
Comparative example 1
Crushing and sieving oil shale to 60mm by using pacifying oil shale, placing 142.5g in a primary pyrolysis unit, and mixing with the mixture containing 4.75g KNO3And 4.75gNa2CO3The bimetallic catalyst is subjected to primary pyrolysis, after the pyrolysis reaction is carried out for 5 hours, the temperature is 480 ℃, the pressure is 28Mpa, a valve is opened, pyrolysis volatile matters enter a secondary pyrolysis unit through a pipeline at 200 ℃, 14250ml of supercritical CO is continuously introduced into the secondary pyrolysis unit2With primary pyrolysis volatiles and pre-conditioned 7.125gFe (NO)3)3And (3) carrying out secondary pyrolysis, reacting for 0.5h at 500 ℃ under 12Mpa, and allowing pyrolysis oil gas of the obtained secondary pyrolysis product to enter a cooling unit and collecting for component analysis. The result is that the pyrolysis oil contains 41% of light oil with C8-C12 atoms; 20% of medium oil with C12-C18, and C atoms>The C19 heavy oil accounted for 39%.
Comparative example 2
The differences from comparative example 1 are: 380ml of supercritical water is continuously introduced into the primary pyrolysis unit without putting 4.75g of KNO3And 4.75gNa2CO3And the other conditions are consistent. As a result, the pyrolysis oil contains 46% of light oil with C8-C12 atoms; 11% of medium oil with C12-C18 atoms, and C atoms>The C19 heavy oil accounted for 43%.
Comparative example 3
The differences from comparative example 1 are: 380ml of supercritical water is continuously introduced into the primary pyrolysis unit, and supercritical CO is not introduced into the secondary pyrolysis unit2And the other conditions are consistent. As a result, the pyrolysis oil is obtained, and the light oil with C atoms of C8-C12 accounts for 52%; the C12-C18 medium oil accounts for 19 percent>The C19 heavy oil accounted for 29%.
Comparative example 4
The differences from comparative example 1 are: 380ml of supercritical water is continuously introduced into the primary pyrolysis unit, and 7.125gFe (NO) is not placed into the secondary pyrolysis unit in advance3)3And the other conditions are consistent. The result is that the light oil with C8-C12 atoms in the pyrolysis oil accounts for 55 percent; the C12-C18 medium oil accounts for 25%, and has C atoms>The C19 heavy oil accounted for 20%.
The results of fig. 2 show that, by comparing comparative examples 1 to 4 with example 3, it can be seen that the method for improving the quality of the oil shale pyrolysis oil through deep pyrolysis can improve the content of the light oil with C8-C12 atoms by 23-37%.
In conclusion, the method for improving the quality of the oil shale pyrolysis oil through deep pyrolysis can effectively improve the quality of the oil shale pyrolysis oil, realizes two-time improvement on the quality of the pyrolysis oil, and has great significance for improving heavy oil.
Claims (6)
1. A method for improving the quality of oil shale pyrolysis oil through deep pyrolysis is characterized by comprising the following steps:
crushing and screening an oil shale sample, and then placing the oil shale sample in a primary pyrolysis unit;
step two, continuously introducing supercritical water dissolved with a bimetallic catalyst into the primary pyrolysis unit, and after carrying out pyrolysis reaction for 1-8h, introducing the obtained pyrolysis volatile matter into a secondary pyrolysis unit in which the catalyst is placed in advance through a pipeline with a heating sleeve; the bimetallic catalyst is any two of sulfate, carbonate, acetate and nitrate of alkali metals K and Na; the catalyst in the secondary pyrolysis unit is one or more of active metal sulfate, carbonate, acetate and nitrate of Ba, fe and Ce; the temperature of the supercritical water is controlled to be 374-500 ℃, and the pressure is controlled to be 23-30 Mpa; the ratio of the mass of the bimetallic catalyst dissolved in supercritical water to the volume of supercritical water is (1;
step three, continuously introducing supercritical CO into the secondary pyrolysis unit2Carrying out secondary pyrolysis with the primary pyrolysis volatile matter and a pre-placed catalyst, reacting for 0.2-1.2h, and cooling and collecting pyrolysis oil gas of an obtained secondary pyrolysis product; the supercritical CO2The temperature is controlled between 410 ℃ and 500 ℃, and the pressure is controlled between 8Mpa and 12Mpa.
2. The method for upgrading oil shale pyrolysis oil by deep pyrolysis of claim 1, wherein: in the second step, the mass ratio of two metal catalysts in the bimetallic catalyst dissolved in supercritical water is 1: (1-5).
3. The method for upgrading oil shale pyrolysis oil by deep pyrolysis according to claim 1 or 2, characterized in that: in the second step, the mass ratio of the bimetallic catalyst to the oil shale sample in the primary pyrolysis unit is 1: (6-15).
4. The method for upgrading oil shale pyrolysis oil by deep pyrolysis according to claim 3, wherein: in the second step, the temperature of the pipeline with the heating jacket is controlled to be 200-300 ℃.
5. The method for upgrading oil shale pyrolysis oil by deep pyrolysis of claim 4, wherein: the mass ratio of the catalyst to the oil shale sample in the secondary pyrolysis unit is 1: (9-20).
6. The method for upgrading oil shale pyrolysis oil by deep pyrolysis according to claim 5, wherein: oil shale sample quality and supercritical CO described in step three2The volume ratio of (1.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4737267A (en) * | 1986-11-12 | 1988-04-12 | Duo-Ex Coproration | Oil shale processing apparatus and method |
| JP2000282063A (en) * | 1999-03-31 | 2000-10-10 | Mitsubishi Materials Corp | Conversion of hydrocarbon resource by using supercritical water |
| JP2002096080A (en) * | 2000-09-21 | 2002-04-02 | Japan Organo Co Ltd | Supercritical water reaction apparatus |
| JP2008173596A (en) * | 2007-01-21 | 2008-07-31 | National Institute Of Advanced Industrial & Technology | Supercritical carbon dioxide-used reaction method and apparatus therefor |
| CN101528336A (en) * | 2006-04-07 | 2009-09-09 | 查特股份有限公司 | Supercritical process, reactor and system for hydrogen production |
| CN102711995A (en) * | 2009-11-11 | 2012-10-03 | 株式会社理光 | Method for producing catalyst-supporting carrier and apparatus for producing same |
| CN104152166A (en) * | 2014-06-11 | 2014-11-19 | 华南理工大学 | Comprehensive utilization system and process for hydrogen production by gasification of oil shale refining integrated associated coal |
| CN107178350A (en) * | 2016-03-09 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of method of hydro carbons in in-situ extraction oil shale |
| CN107847991A (en) * | 2015-04-13 | 2018-03-27 | 阿基米德有限责任公司 | Equipment and correlation technique for Waste disposal |
| CN110982550A (en) * | 2019-12-10 | 2020-04-10 | 重庆工商大学 | Catalytic pyrolysis treatment method and test device for shale gas exploitation oil-based drilling cuttings |
| CN111788284A (en) * | 2018-02-26 | 2020-10-16 | 沙特阿拉伯石油公司 | Additive for supercritical water process for upgrading heavy oil |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1034763A (en) * | 1973-12-28 | 1978-07-18 | Bernard L. Schulman | Integrated coking and catalytic steam gasification process |
| JP2000109850A (en) * | 1998-10-07 | 2000-04-18 | Mitsubishi Materials Corp | Process and device for converting heavy oil into fluid fuel for generating unit |
| US7780763B2 (en) * | 2007-02-15 | 2010-08-24 | Chung-Sung Tan | Method of desorbing a volatile component from a spent adsorbent with rotating packed bed and method of recovering 2,2,3,3-tetrafluro-1-propanol from a gas stream by adsorption |
| US9796648B2 (en) * | 2014-05-02 | 2017-10-24 | University Of Tennessee Research Foundation | Glycerol dehydration methods and products thereof |
| EP3820970A4 (en) * | 2018-07-10 | 2022-06-01 | Iogen Corporation | Method and system for producing a fuel from biogas |
| CN113621399B (en) * | 2021-08-20 | 2022-09-09 | 太原理工大学 | Supercritical water-oxygen reaction device for L-shaped powder or block organic rock and use method thereof |
-
2022
- 2022-07-14 CN CN202210826985.8A patent/CN114921257B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4737267A (en) * | 1986-11-12 | 1988-04-12 | Duo-Ex Coproration | Oil shale processing apparatus and method |
| JP2000282063A (en) * | 1999-03-31 | 2000-10-10 | Mitsubishi Materials Corp | Conversion of hydrocarbon resource by using supercritical water |
| JP2002096080A (en) * | 2000-09-21 | 2002-04-02 | Japan Organo Co Ltd | Supercritical water reaction apparatus |
| CN101528336A (en) * | 2006-04-07 | 2009-09-09 | 查特股份有限公司 | Supercritical process, reactor and system for hydrogen production |
| JP2008173596A (en) * | 2007-01-21 | 2008-07-31 | National Institute Of Advanced Industrial & Technology | Supercritical carbon dioxide-used reaction method and apparatus therefor |
| CN102711995A (en) * | 2009-11-11 | 2012-10-03 | 株式会社理光 | Method for producing catalyst-supporting carrier and apparatus for producing same |
| CN104152166A (en) * | 2014-06-11 | 2014-11-19 | 华南理工大学 | Comprehensive utilization system and process for hydrogen production by gasification of oil shale refining integrated associated coal |
| CN107847991A (en) * | 2015-04-13 | 2018-03-27 | 阿基米德有限责任公司 | Equipment and correlation technique for Waste disposal |
| CN107178350A (en) * | 2016-03-09 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of method of hydro carbons in in-situ extraction oil shale |
| CN111788284A (en) * | 2018-02-26 | 2020-10-16 | 沙特阿拉伯石油公司 | Additive for supercritical water process for upgrading heavy oil |
| CN110982550A (en) * | 2019-12-10 | 2020-04-10 | 重庆工商大学 | Catalytic pyrolysis treatment method and test device for shale gas exploitation oil-based drilling cuttings |
Non-Patent Citations (3)
| Title |
|---|
| A review on the upgradation techniques of pyrolysis oil;Anjani R.K.Gollakota;《Renewable and Sustainable Energy Reviews》;20160202;第58卷;121-132 * |
| 吉林桦甸油页岩原位近临界水热解开采室内实验;马中良;《科学技术与工程》;20160428(第12期);23-28 * |
| 超临界流体技术及其在石油化工中的应用;李会鹏等;《抚顺石油学院学报》;19980325(第01期);32-38 * |
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